EP2730424B1 - Procédé d'enregistrement à jet d'encre - Google Patents

Procédé d'enregistrement à jet d'encre Download PDF

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Publication number
EP2730424B1
EP2730424B1 EP13185575.1A EP13185575A EP2730424B1 EP 2730424 B1 EP2730424 B1 EP 2730424B1 EP 13185575 A EP13185575 A EP 13185575A EP 2730424 B1 EP2730424 B1 EP 2730424B1
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EP
European Patent Office
Prior art keywords
white color
color
ink composition
image
resin
Prior art date
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Active
Application number
EP13185575.1A
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German (de)
English (en)
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EP2730424A1 (fr
Inventor
Hitoshi Ohta
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Seiko Epson Corp
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Seiko Epson Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J11/00—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form
    • B41J11/0015—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form for treating before, during or after printing or for uniform coating or laminating the copy material before or after printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/008—Sequential or multiple printing, e.g. on previously printed background; Mirror printing; Recto-verso printing; using a combination of different printing techniques; Printing of patterns visible in reflection and by transparency; by superposing printed artifacts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0023—Digital printing methods characterised by the inks used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/009—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using thermal means, e.g. infrared radiation, heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0064—Digital printing on surfaces other than ordinary paper on plastics, horn, rubber, or other organic polymers

Definitions

  • the present invention relates to an ink jet recording method.
  • JP-A-2007-277380 describes that by using an energy ray-curable ink including water, a photopolymerizable compound, a photopolymerization initiator and the like, printing with respect to the recording medium with ink non-absorbability is performed. Since such an energy ray-curable ink is cured by irradiation of energy rays, the energy ray-curable ink can be fixed on the recording medium with ink non-absorbability such as a plastic film, also.
  • a flexible packing film is widely used for packing foods or the like.
  • the flexible packing film is used for displaying product names and the like of products to be packed, and has a recording surface (formed of, for example, plastic materials such as polyolefin, nylon, polyester, and the like) on which images are printed.
  • Gravure printing is commonly used for printing with respect to the recording surface of the flexible packing film, and a gravure ink which is used in the gravure printing is obtained by dispersing or dissolving components such as pigments and resins in organic solvents (refer to JP-A-2012-46587 ).
  • the energy ray-curable ink uses the photopolymerizable compound and the photopolymerization initiator, there is a case that it may not be the case that the effect on the reduction of environmental load is sufficient. Furthermore, since the mechanism for irradiating light is necessary to cure the energy ray-curable ink, problems such as the increase in size of an ink jet recording apparatus and the increase of power consumption, the complexification of light irradiation control and the like have occurred.
  • the flexible packing film is widely used in packing foods, reducing the consumption of components such as organic solvents, photopolymerizable compounds, photopolymerization initiators and the like to minimize the effect on the human body is demanded.
  • a water-based ink for an ink jet recording of which a main solvent is water is being developed to solve the problems described above, however, images obtained by recording the water-based ink in the related art on the flexible packing film do not have sufficient abrasion resistance and sufficient peeling resistance yet.
  • US 2011/184108 discloses a white ink composition that contains a white coloring material and a fixing resin component.
  • the fixing resin component includes a styrene acrylic resin and a urethane resin at a mass ratio of the styrene acrylic resin to the urethane resin (styrene acrylic resin/urethane resin) of at least 1/10.
  • This document further discloses on inkjet recording method comprising recording a white color based image and a color image.
  • An advantage of the present invention is to provide an inkjet recording method which may record images with excellent abrasion resistance and excellent peeling resistance.
  • an ink jet recording method as defined in claim 1.
  • image in an aspect of the invention indicates a printing pattern formed from a dot group and includes text printing and solid printing.
  • the Figure is a schematic diagram showing an example of an ink jet recording apparatus in an ink jet recording method according to an embodiment of the invention.
  • An ink jet recording method according to the present invention is defined in claim 1.
  • the ink jet recording method includes the white color-based image recording step.
  • the white color-based image recording step is a step in which by discharging droplets of the white color-based ink composition (described below) from the nozzles of the ink jet recording head, and by attaching the droplets of the white color-based ink composition on the recording surface of the flexible packing film, the white color-based image is recorded.
  • the ink jet recording method may include a white color-based image heating step in which the white color-based image is heated to a temperature in the range of 40°C to 80°C before the color image recording step described below.
  • the white color-based image heating step corresponds to the third heating step in aspects.
  • the heating temperature in the white color-based image heating step is 40°C to 80°C, and is preferably 60°C to 80°C.
  • the white color-based image heating step when used in the heating of the white color-based image on the recording surface of the flexible packing film, may be a step which heats droplets during flying (during discharging) of the droplets of the white color-based ink composition. That is, the white color-based image heating step may be performed successively, before forming, during forming, and/or after forming the white color-based image.
  • the heating temperature according to an aspect of the invention refers to the surface temperature of the recording surface of the flexible packing film.
  • a measuring method for surface temperature is not particularly limited, but, thermography using thermography apparatus H2640/H2630 (NEC Avio Infrared Technologies Co., Ltd.) may be used, for example.
  • the ink jet recording method includes the color image recording step.
  • the color image recording step is a step in which by discharging droplets of the color ink composition from the nozzles, and by attaching the droplets of the color ink composition on the white color-based image, the color image is recorded. In the above described manner, the color image is formed on at least a portion of the white color-based image.
  • the abrasion resistance and the peeling resistance are excellent compared to those in a case where the image is formed on the flexible packing film directly.
  • the color image recording step is preferably performed when the mass is in the range of 30% to 80% by drying of the white color-based image. Furthermore, it is more preferably performed when the mass is set to be in the range of 35% to 75%.
  • the mass after the drying of the white color-based image is in the above-ranges, particularly not greater than the upper limit, it is possible to suppress the mixing of the white color-based image and the color image, and thus a clear color image may be obtained.
  • the mass after drying of the white color-based image is in the above-range, particularly not less than the lower limit, it is possible to maintain the adhesion between the white color-based image and the flexible packing film, and thus the adhesion between the white color-based image and the color image may be improved. Furthermore, in a case where the color ink composition includes a resin different from that in the white ink composition, thermal contraction and the like of the resin which is included in each ink are different, and thus peeling-off is likely to occur more notably than at the interface between the white color-based image and the color image.
  • the ink jet recording method may, further, include a color image heating step in which the color image is heated.
  • a color image heating step in which the color image is heated.
  • the color image heating step may be performed successively after the white color-based image heating step, before forming the color image, and during forming the color image.
  • the heating temperature of the color image heating step is preferably 40°C or more, is more preferably 40°C to 80°C, and is even more preferably 40°C to 60°C.
  • the ink jet recording method may, further, include a coating step.
  • the coating step is a step in which the color image is coated with coating film formed of the resin ink composition. Since coating the color image with coating film may suppress the generation of peeling and abrasion of the color image and the white color-based image, it is possible to improve the abrasion resistance and the peeling resistance of the image which is recorded on the flexible packing film.
  • the coating film may coat at least the upper surface of the color image, and may continuously coat the side surface from the upper surface of the color image, further, may continuously coat to the upper surface of the white color-based image on which the color image is not recorded.
  • the fixity of the coating film is further improved. This is preferable since the abrasion resistance and the peeling resistance of the color image and the white color-based image are further improved.
  • the coating step is preferably performed in the mass range of 30% to 80% after drying of the color image. Maintaining the mass in the mass range of 35% to 75% is more preferable since the color mixing with the coating film in the coating step and the adhesion may become in an excellent state.
  • the resin ink composition includes a resin different from that in the color ink composition
  • thermal contraction and the like of the resin which is included in each ink are different, peeling-off is likely to occur more notably at the interface between the color image and the coating film.
  • by performing recording in the partially dried state described above mixing of the ink compositions to each other at the interface between the color image and the coating film occurs, and even when both the ink compositions partly contain different resin, it is possible to suppress the defects of peeling-off and the like.
  • a natural drying may be sufficient, but in accordance with the image heating described above, it is possible to improve the recording speed.
  • the ink jet recording method may include a coating film heating step in which the coating film is heated to a temperature of 40°C or higher before an entire heating step described below.
  • the coating film heating step corresponds to a second heating step in aspects.
  • the heating temperature in the coating film heating step is usually 40°C or higher, and is preferably 40°C to 60°C. Thus, it is possible to suppress distortion and contraction of the flexible packing film, and for part of volatile components in the coating film to be evaporated and scattered efficiently.
  • the color mixing with the coating film on the color image and the adhesion may become in an excellent state, by performing the coating film heating step before forming the coating film and/or during forming, performing the coating film heating step before forming the coating film and/or during forming is preferable.
  • the third heating step white color-based image heating step
  • the color image heating step from after the end of the white color-based image recording to after the end of the color image recording may be called the color image heating step
  • the end of the color image recording to the coating step corresponds to the coating film heating step (and may be called the second heating step).
  • the ink jet recording method includes an entire heating step which heats at least the white color-based image and the color image to a temperature higher than 40°C.
  • the entire heating step is a step in which, in addition to the white color-based image and the color image, the coating film is heated as well.
  • the entire heating step corresponds to the first heating step in aspects.
  • the heating temperature in the entire heating step is higher than 40°C, is preferably from higher than 40°C to 80°C, and is more preferably 60°C to 80°C.
  • the heating temperature in the entire heating step is higher than 40°C, filming and/or drying of the white color-based image, the color ink images which are recorded on the flexible packing film, and the coating film may be promoted.
  • the temperature is 80°C or lower, the distortion of the flexible packing film may be suppressed.
  • the heating temperature of the entire heating step is preferably higher than the heating temperature in the white color-based image heating step.
  • the heating temperature in the entire heating step is preferably higher than the heating temperature in the color image heating step and the coating film heating step.
  • the heating time in the entire heating step is preferably longer than heating time in the white color-based image heating step.
  • the heating time in the entire heating step is preferably longer than that of the color image heating step and the coating film heating step.
  • the ink jet recording method may further include a hydrophilicity treating step. Since, when the hydrophilicity treating step is performed, the adhesion of the image which is recorded is improved, there is a case where the abrasion resistance and the peeling resistance of the image which is recorded may be improved.
  • the hydrophilicity treating step may be performed with respect to the recording surface of the flexible packing film (a) before the white color-based image recording step, (b) may be performed with respect to the white color-based image before the color image recording step after the white color-based image recording step, and (c) may be performed with respect to the color image before the coating step after the color image recording step.
  • a hydrophilic treatment may be performed using a well-known corona discharge treatment apparatus and a plasma discharge treatment apparatus.
  • an example of an ink jet recording apparatus which may be suitably used in the ink jet recording method described above will be exemplified.
  • the ink jet recording apparatus which may be used in the inkjet recording method according to the invention is not limited to the following aspects.
  • the Figure is a schematic diagram showing an example of the ink jet recording apparatus used in the ink jet recording method of the present invention.
  • a ink jet recording apparatus 1000 which is an example is configured to have a transporting unit 10 which transports a flexible packing film 1, a white color-based image recording unit 20 which records the white color-based image using the white color-based ink composition, a white color-based image heating unit 25 which is provided at the position facing the white color-based image recording unit, a color image recording unit 120 which records the color image on the white color-based image using the color ink composition, a color image heating unit 125 which is provided at the position facing the color image recording unit, a coating unit 220 which forms a coating film which coats the color image using the resin ink composition, a coating film heating unit 225 which is provided at the position facing the coating unit, and an entire heating unit 235 which heats the white color-based image, the color image, and the coating film.
  • a transporting unit 10 which transports a flexible packing film 1
  • a white color-based image recording unit 20 which records the white color-based image using the white color-based ink composition
  • the white color-based image heating unit and the color image heating unit may respectively be, if necessary, provided with a white color-based image heating unit 35 which is employed at the downstream side of the white color-based image heating unit 25, and a color image heating unit 135 which is employed at the downstream side of the color image heating unit 125.
  • the transporting unit 10 may be configured from a roller 11.
  • the transporting unit 10 may have a plurality of rollers 11.
  • the transporting unit 10 in the direction to which the flexible packing film 1 is transported (indicated by arrows in the figure), is provided at the upstream side of the white color-based image recording unit 20, however, it is not limited thereto.
  • the position provided and the number of positions are arbitrary.
  • the transporting unit 10 may be provided with a paper feeding roll, a paper feeding tray, a paper output roll, a paper output tray, various types of platen and the like.
  • the flexible packing film 1 which is transported by the transporting unit 10 is transported to the position where the white color-based image is recorded on the recording surface by the white color-based image recording unit 20.
  • the Figure illustrates a case in which the flexible packing film 1 is a roll.
  • the flexible packing film 1 is a single sheet, it is possible to perform the transportation of the flexible packing film by suitably configuring the transporting unit 10.
  • the white color-based image recording unit 20 records a white color-based image 2 using the white color-based ink composition with respect to the recording surface of the flexible packing film 1.
  • the white color-based image recording unit 20 is provided with an ink jet recording head 21 which has nozzles which discharge the white color-based ink composition.
  • the white color-based image recording unit 20 is one example of unit in order to perform the white color-based image recording step described above.
  • examples of the methods include a method in which a strong electric field is applied between the nozzles and an accelerating electrode placed in front of the nozzles, the ink composition in liquid droplet shape from the nozzle is continuously discharged, and during flying between the deflecting electrodes of the liquid droplets of the ink composition, by sending a recording information signal to the deflecting electrodes, or discharging according to the recording information signal without deflecting the liquid droplets of the ink composition, recording is performed (electrostatic attraction method); a method in which by applying pressure to the ink composition using a small pump, and mechanically vibrating the nozzles using a quartz oscillator or the like, the liquid droplets of the ink composition are forcibly discharged; a method in which pressure and the recording information signal are applied to the ink composition by a piezo
  • the white color-based image heating unit heats the white color-based image 2.
  • the white color-based image heating unit 25 is employed at the position facing the white color-based image recording unit 20.
  • the white color-based image heating unit 25 is not particularly limited, as long as the configuration in which evaporation and scattering of the liquid medium which is present in the white color-based ink composition is promoted is provided.
  • the white color-based image heating unit 25 is one example of a unit in order to perform the white color-based image heating step described above.
  • the white color-based image heating unit 35 may be provided at the downstream side of the white color-based image heating unit 25.
  • the white color-based image heating unit 25, and the white color-based image heating unit 35 include a unit in which a platen heater is provided below (the opposite side of the flexible packing film 1 when viewed from the transporting surface) the transporting surface of the flexible packing film 1, and heats the flexible packing film 1 from the opposite side to the recording surface; a unit in which a heating chamber or a thermostatic oven in which the flexible packing film 1 is immersed during transportation is provided, and heats the flexible packing film 1 from various directions; a unit in which a heater is provided above the transporting surface of the flexible packing film 1, and heats the flexible packing film 1 from the side of the recording surface; and the like.
  • the heater including the platen heater, the heating chamber, and the type of the thermostatic oven are not limited, however, forced air heating, radiation heating, conduction heating, high-frequency drying, microwave drying, and the like may be used, for example.
  • the color image recording unit 120 records the color image (not shown in the figure) using the color ink composition on the white color-based image 2.
  • the color image recording unit 120 is one example of a unit in order to perform the color image recording step described a bove.
  • the placed position is not limited, however, for example, it may be placed at the downstream side of the white color-based image recording unit 20.
  • the color image recording unit 120 is provided with an ink jet recording head 121 which has the nozzles which discharges the color ink composition.
  • the method for discharging the color ink composition from the nozzles of the ink jet recording head 121 is the same as that in one of the examples described in the white color-based image recording unit 20, and thus, the description thereof will not be repeated.
  • the color image heating unit heats the color image (not shown).
  • the color image heating unit 125 is employed at the position facing the color image recording unit 120.
  • the color image heating unit 125 is one example of a unit in order to perform the color image heating step described above.
  • the placed position is not limited, however, it may be placed at the downstream side of the white color-based image heating unit, for example.
  • the color image heating unit 135 may be provided at the downstream side of the color image heating unit 125.
  • the heating unit used in the color image heating unit 125 and the color image heating unit 135, the heating unit may be one described for the white color-based image heating unit 25 and the white color-based image heating unit 35.
  • the coating unit 220 forms the coating film (not shown) which coats the color image using the resin ink composition.
  • the coating unit 220 is one example of a unit in order to perform the coating step described above.
  • the coating unit 220 is provided with an inkjet recording head 221 which has nozzles which discharge the resin ink composition.
  • the method for discharging the resin ink composition from the nozzles of an ink jet recording head 131 is the same as that in one of the examples described in the white color-based image recording unit 20. Thus, the description thereof will not be repeated.
  • the placed position is not particularly limited, however, it may be placed at the downstream side of the color image recording unit 120, for example.
  • the coating unit 220 may also be combined with the color image recording unit 120.
  • the nozzles for discharging the color ink composition, and the nozzles for discharging the resin ink composition may be mounted on one ink jet recording head.
  • a coating film heating unit 225 heats the coating film (not shown).
  • the coating film heating unit 225 is one example of a unit in order to perform the coating film heating step described above.
  • the placed position is not limited, however, it may be placed at the downstream side of the color image heating unit, for example.
  • the heating unit used in the coating film heating unit 225 may be one described for the white color-based image heating unit 25 and the white color-based image heating unit 35.
  • the coating unit 220 adopts the ink jet printing system is shown in the ink jet recording apparatus 1000 according to the embodiment.
  • a coating method which uses a roll coater or the like may be adopted.
  • the entire heating unit 235 heats the white color-based image, the color image, and the coating film.
  • the entire heating unit 235 is one example of a unit in order to perform the entire heating step described above.
  • the placed position is not limited. It may be placed at the downstream side of the coating unit 220 as in the example in the Figure.
  • the heating unit used in the entire heating unit 235 one described for the white color-based image heating unit 25 and the white color-based image heating unit 35 may be used.
  • the ink jet recording apparatus 1000 may further include a hydrophilic treatment unit.
  • the hydrophilic treatment unit for example, is configured from a well-known corona discharge treatment apparatus or a plasma discharge treatment apparatus.
  • the white color-based ink composition, and the color ink composition are used in the ink jet recording method according to the invention.
  • the components which are included in each ink composition will be described in detail.
  • the white color-based ink composition which is used in the ink jet recording method according to the invention contains a coloring material of the white color base, a urethane-based resin and water.
  • the white color-based ink composition means an ink which may record a color referred to as “white” in common sense, and the white color-based ink composition may also contain one which is colored with trace amount. Furthermore, the ink which contains the pigment includes an ink which is called “white ink” or the like, and commercially available.
  • the coloring material of the white color base examples include metal oxides, barium sulfate, calcium carbonate, and the like.
  • the metal oxides include titanium dioxide, zinc oxide, silica, alumina, magnesium oxide, and the like.
  • the coloring material of the white color base includes particles having a hollow structure.
  • the particles having a hollow structure are not particularly limited, and a well-known one in the related art may be used.
  • the particles described in the specification of U.S. Patent No.4,880,465 may be preferably used as the particles having the hollow structure.
  • titanium dioxide is preferable as the coloring material of the white color base which is contained in the white color-based ink composition used in the method of an embodiment of the invention.
  • the content of the coloring material of the white color base (solid content) is preferably 1% by mass to 20% by mass, and is more preferably 5% by mass to 15% by mass, with respect to the total mass of the white color-based ink composition.
  • the content of the coloring material of the white color base is in the above range, particularly, not more than the upper limit, there is a case where the discharge stability of the nozzles of the ink jet recording apparatus becomes excellent.
  • the content of the coloring material of the white color base is in the above range, particularly, not less than the lower limit, there is a tendency that an excellent image having high color density such as the degree of pure whiteness may be obtained.
  • the average particle diameter of the coloring material of the white color base on the basis of volume (hereinafter, referred to as "average particle diameter") is preferably 30 nm to 600 nm, and is more preferably 200 nm to 400 nm.
  • average particle diameter of the coloring material of the white color base is in the above range, and particularly, is not more than the upper limit, there is a case where dispersion stability of particles which form the coloring material of the white color base becomes excellent, and the discharge stability of the nozzles of the ink jet recording apparatus becomes excellent.
  • the average particle diameter of the coloring material of the white color base is in the above range, and particularly, not less than the lower limit, there is a tendency that pure whiteness becomes high.
  • the average particle diameter of the coloring material of the white color base may be measured by particle size distribution measuring apparatus which uses a laser diffraction scattering method as the measurement principle.
  • An example of the particle size distribution measuring apparatus includes a particle size distribution analyzer (for example, "Microtrac UPA” manufactured by Nikkiso Co., Ltd.) which uses a dynamic light scattering method as the measurement principle.
  • the urethane-based resin improves the fixity of the white color-based ink composition with respect to the flexible packing film, and can make the abrasion resistance and the peeling resistance of the white color-based image which is recorded on the flexible packing film excellent.
  • the mechanism in detail is not clear, but it is considered that the following reason becomes one factor.
  • an anti-fogging agent and an antistatic agent are present on the recording surface of the flexible packing film.
  • the anti-fogging agent and the antistatic agent have a fat-soluble surfactant (will be described later) as a main component, and in many cases, are formed of low molecules with high polarity. Therefore, when a styrene-acrylic resin which has been used in a water-based ink in the related art is used, since the anti-fogging agent and the antistatic agent become a peeling-off layer of ink, the fixity of an image is decreased.
  • the urethane-based resin has many polar groups compared to the styrene-acrylic resin, it is considered that, by dissolving the anti-fogging agent and the antistatic agent together, an image may be firmly fixed on the recording surface of the flexible packing film.
  • the urethane-based resin is a polymer which is synthesized by the reaction of polyisocyanate and polyol.
  • the synthesis of the urethane-based resin may be performed using well-known methods in the related art.
  • polyisocyanate examples include: a linear aliphatic isocyanate such as tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysine diisocyanate, and the like; an aliphatic isocyanate having a cyclic structure such as 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate; aromatic isocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diis
  • polyol examples include polyether polyol and polycarbonate polyol and the like.
  • polyether polyol examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.
  • polycarbonate polyol examples include diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, or polytetramethylene glycol, and the like and phosgene, dialkyl carbonates such as dimethyl carbonate, and the like or the reaction products of ethylene carbonate, and the like with cyclic carbonates.
  • the emulsion type in which the above described urethane-based resin is dispersed as in powder shape is preferably used.
  • urethane-based resin of an emulsion type commercially available products may be used.
  • examples of the urethane-based resin of the emulsion type include Superflex 130,740 (trade name, manufactured by DAI-ICHI KOGYO SEIYAKU CO., LTD.), RESAMINE D-1060, D-2020, D-4080, D-4200, D-6300, D-6455 (trade name, manufactured by Dainichiseika Color & Chemicals Mfg. Co.
  • the glass-transition temperature Tg of the urethane-based resin is preferably 10°C to 70°C, is more preferably 10°C to 60°C, and is even more preferably 15°C to 60°C.
  • Tg of the urethane-based resin is in the above-range, and particularly not less than the lower limit, while imparting a moderate flexibility to coating of the white color-based image, it is possible to improve the abrasion resistance of the white color-based image.
  • Tg of the urethane-based resin is in the above-range, and particularly not more than the upper limit, since coating of the white color-based image may be firm, while suppressing the embrittlement of the film, it is possible to improve the peeling resistance of the white color-based image.
  • the content of the urethane-based resin is preferably 0.1% by mass to 30% by mass, is more preferably 0.5% by mass to 20% by mass, and is particularly preferably 1% by mass to 15% by mass in terms of solid content, with respect to the entire ink composition.
  • the content of the urethane-based resin is in the above range, particularly, not less than the lower limit, it is possible to further improve the abrasion resistance and the peeling resistance of the white color-based image.
  • the content of the urethane-based resin is in the above-range, particularly not more than the upper limit, there is a tendency that the preservation stability and the discharge stability of the white color-based ink composition become excellent.
  • Water is a main medium of the white color-based ink composition, and a component which is evaporated and scattered by drying.
  • Water is preferably pure water such as ion-exchanged water, ultrafiltration water, reverse osmosis water, and distilled water, or a water in which ionic impurity is removed as much as possible, such as ultrapure water.
  • a pigment dispersion and the ink composition formed of the pigment dispersion are stored for a long time, the generation of mold and bacteria can be prevented, and therefore using water which is sterilized by UV irradiation or addition of hydrogen peroxide is preferable.
  • the white color-based ink composition according to an embodiment is, so called, a water-based ink which includes water as a main solvent (water is contained as much as 50% by mass or more).
  • the water-based ink has advantages that odor may be suppressed. Also, it is good for the environment since the water makes up 50% by mass or more of the composition.
  • the white color-based ink composition according to an embodiment may, further, contain one or more of wax, surfactant, alkyl polyols, glycol ethers, pyrrolidones, a pH adjusting agent, a preservative and fungicide, an anti-corrosion agent, a chelating agent, and the like.
  • wax surfactant
  • alkyl polyols glycol ethers
  • pyrrolidones a pH adjusting agent
  • a preservative and fungicide an anti-corrosion agent
  • a chelating agent and the like.
  • Wax imparts lubricity and gloss to the surface of the recorded image. Thus, the generation of peeling-off, and friction and the like of images may be suppressed.
  • the use of wax with a higher melting point than the heating temperature in the entire heating step described above is preferable. In the above-described manner, since the wax remains without melting out, it is possible to suppress the decrease of characteristics of the wax, and then the abrasion resistance and the peeling resistance of the white color-based image become excellent.
  • Examples of the components which configure the wax include plant and animal waxes such as carnauba wax, candeilla wax, beeswax, rice wax, lanolin; petroleum-base waxes such as paraffin wax, microcrystalline wax, polyethylene wax, oxidized polyethylene wax, petrolatum; mineral-based waxes such as montan wax, ozokerite; synthetic waxes such as carbon wax, Hoechst wax, polyolefin wax, stearic acid amide, natural-synthetic wax emulsion and blended wax such as ⁇ -olefin-maleic anhydride copolymer.
  • the waxes may be singly used, or may be used as a mixture of two or more kinds.
  • polyolefin waxes in particular, polyethylene wax, and polypropylene wax
  • paraffin wax is preferable.
  • waxes may be also used as they are.
  • examples of the waxes include Nopukoto PEM-17 (trade name, manufactured by San Nopco Co., Ltd.), CHEMIPEARL W4005 (trade name, manufactured by Mitsui Chemicals, Inc.), and AQUACER515, 539, 593 (all are trade names, manufactured by BYK Japan KK) and the like.
  • the content of the wax is preferably 0.1% by mass to 5% by mass in terms of solid content, with respect to the total mass of the white color-based ink composition.
  • the content of the wax is in the above range, the function of the above wax may be exhibited excellently.
  • a surfactant has a function that uniformly wets and distributes the ink composition on the recording medium (flexible packing film).
  • nonionic surfactants are preferable.
  • silicone-based surfactants, acetylene glycol-based surfactants, and polyoxy ethylene alkyl ether-based surfactants are more preferable.
  • silicone-based surfactants polysiloxane-based compounds are preferably used, and polyether-modified organosiloxane, and the like are exemplified. More specifically, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK-348 (all are trade names, manufactured by BYK Japan KK), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017 (all are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like are exemplified.
  • the content is preferably 0.1% by mass to 5% by mass with respect to the total amount of the white color-based ink composition.
  • Acetylene glycol-based surfactants are excellent in surface tension and have an ability to suitably retain surface tension, and have the characteristic of no or low foaming property.
  • an ink composition which contains an acetylene glycol-based surfactant may suitably retain surface tension and interfacial tension between the ink composition of a head nozzle surface and a printer member which contacts thereto, and when the surfactant is applied to the ink jet recording method, it is possible to significantly enhance the discharge stability.
  • acetylene glycol-based surfactant for example, SURFYNOL 104, 104 E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, DF110D (all are trade names, manufactured by Air Products and Chemicals Inc), Olfine B, Y, P, A, STG, SPC, E1004, E1010, PD-001, PD-002W, PD-003, PD-004, EXP.4001, EXP.4036, EXP.4051, AF-103, AF-104, AK-02, SK-14, AE-3 (all are trade names, manufactured by Nissin Chemical Industry Co., Ltd.), acetylenol E00, E00P, E40, E100 (all are trade names,
  • the content is preferably 0.1% by mass to 5% by mass with respect to the total amount of the white color-based ink composition.
  • Polyoxyethylene alkyl ether-based surfactants are excellent, in particular, in ability to be arrayed on the interface of the ink composition according to an aspect of the invention in comparison to other nonionic surfactants. Accordingly, the surfactant is arrayed on the surface of a dispersion component which is used in the ink composition such as the pigment or the resin emulsion according to an aspect of the invention, and is present at the interface between each component, and thus the dispersion stability to a liquid component of the dispersion component is improved.
  • a dispersion component which is used in the ink composition such as the pigment or the resin emulsion according to an aspect of the invention
  • the surfactant is highly likely to be arrayed at interface between the ink composition and air
  • the white color-based ink composition which contains polyoxy ethylene alkyl ether-based surfactant, in the portion at which the ink composition of the head nozzles and the like contacts with air, suppresses a rapid drying of the ink composition, and action which suppresses nozzle clogging and the like is excellent. Therefore, in a case where the surfactant is applied to the ink jet recording method, it is possible to significantly enhance the discharge stability.
  • the content is preferably 0.1% by mass to 5% by mass, is more preferably 0.5% by mass to 2% by mass, and is particularly preferably 0.5% by mass to 1.5% by mass with respect to the total mass of the white color-based ink composition.
  • the content of polyoxyethylene alkyl ether-based surfactant is in the above-range, particularly not less than the lower limit, it is possible to make the discharge stability of the ink composition excellent.
  • the content of polyoxyethylene alkyl ether-based surfactant is in the above-range, particularly not more than the upper limit, it is possible to suppress the decrease of water resistance of an image which is recorded, and obtain an image which has an excellent water-friction resistance.
  • the white color-based ink composition according to an embodiment may contain one or more alkyl polyols of which the normal boiling point is 180°C to 230°C.
  • alkyl polyols of which the boiling point is in the above-range there is a case where the suppression of the wet-spreading property, and the drying property of the white color-based ink composition is easier.
  • alkyl polyols of which the normal boiling point is 180°C to 230°C are preferable, and alkyl polyols of which the normal boiling point is 188°C to 230°C are more preferable.
  • the normal boiling point of alkyl polyols is in the above-range, particularly in not less than the lower limit, a moisture-retaining property of the white color-based ink composition is excellent, the suppression of clogging of nozzles is easy, which is preferable.
  • the normal boiling point of the alkyl polyols is in the above-range, particularly not more than the upper limit, without greatly decreasing the drying property of the white color-based ink composition, the suppression of the shade unevenness of an image, and the decrease of the fixity of an image are possible, which is preferable.
  • alkyl polyols of which the normal boiling point is 180°C to 230°C include propylene glycol [188°C], dipropylene glycol [230°C], 1,2-butanediol [194°C], 1,2-pentanediol [210°C], 1,2-hexanediol [224°C], 1,2-heptane diol [227°C], 3-methyl-1,3-butanediol [203°C], 2-ethyl-2-methyl-1,3-propanediol [226°C], 2-methyl-1,3-propanediol [214°C], 2-methyl-2-propyl-1,3-propanediol [230°C], 2,2-dimethyl-1,3-propanediol [210°C], 2-methyl pentan-2,4-diol [197°C]. Moreover, the number in parenthesis indicates the normal boiling point.
  • An alkyl polyol of which the normal boiling point is 180°C to 230°C may be solely used, or a mixture of two or more may be used.
  • the content of the alkyl polyols is preferably in the range of 8% by mass to 25% by mass with respect to the total mass of the white color-based ink composition.
  • the preservation stability of the white color-based ink composition and the moisture-retaining property of the white color-based ink composition become excellent, and it is possible to decrease the generation of clogging of the nozzles, which is preferable.
  • the content of the alkyl polyols is in the above-range, particularly not more than the upper limit, without greatly decreasing the drying property of the white color-based ink composition, an image in which the generation of the shade unevenness is small and which has excellent fixity is obtained, which is preferable.
  • the white color-based ink composition substantially does not contain alkyl polyols of which the normal boiling point is 280°C or more.
  • the drying property of the white color-based ink composition is greatly decreased.
  • the alkyl polyols of which the normal boiling point is 280°C or more glycerine (the normal boiling point is 290°C) is exemplified.
  • substantially does not contain A means that A is not intentionally added when manufacturing the ink, and trace amount of A which is inevitably mixed or generated during manufacturing the ink or storing the ink may be included.
  • substantially does not contain A for example, 1.0% by mass or more is not contained, preferably 0.5% by mass or more is not contained, more preferably 0.1% by mass or more is not contained, even more preferably 0.05% by mass or more is not contained, and particularly preferably 0.01% by mass or more is not contained.
  • glycol ether examples include ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monoisohexyl ether, diethylene glycol monohexyl ether, triethylene glycol monohexyl ether, diethylene glycol monoisohexyl ether, triethylene glycol monoisohexyl ether, ethylene glycol monoisoheptyl ether, diethylene glycol isobutyl heptyl ether, triethylene glycol monoisoheptyl ether, ethylene glycol monooctyl ether, ethylene glycol monoisooctyl ether, diethylene glycol monoisooctyl ether, triethylene glycol monoisooctyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, triethylene glycol mono-2-ethylhexyl ether,
  • the alkyl group, which is included in the glycol ether, having a branched structure is more preferable.
  • the glycol ethers in which the alkyl group has a branched structure it is possible to record a clear image with less shade unevenness with respect to the recording surface which includes a polyolefin.
  • glycol ethers include ethylene glycol monoisobutyl ether, ethylene glycol monoisohexyl ether, diethylene glycol monoisohexyl ether, triethylene glycol monoisohexyl ether, ethylene glycol monoisoheptyl ether, diethylene glycol monoisoheptyl ether, triethylene glycol monoisoheptyl ether, ethylene glycol monoisooctyl ether, diethylene glycol monoisooctyl ether, triethylene glycol monoisooctyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, triethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethyl pentyl ether, ethylene glycol mono-2-ethyl pentyl ether, ethylene glycol mono-2-ethyl pentyl
  • 2-methylpentyl group, 2-ethylpentyl group, and 2-ethylhexyl group are more preferable; and 2-ethylhexyl group is particularly preferable.
  • ethylene glycol mono-2-ethylhexyl ether diethylene glycol mono-2-ethylhexyl ether, triethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylpentyl ether, ethylene glycol mono-2-ethylpentyl ether, ethylene glycol mono-2-methyl pentyl ether, diethylene glycol mono-2-methyl pentyl ether, and the like are exemplified.
  • Ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, triethylene glycol mono-2-ethylhexyl ether, and the like are particularly preferable.
  • the pyrrolidones may be used from the viewpoint of increasing the fixity of the ink composition.
  • As the pyrrolidones N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-pyrrolidone, N-butyl-2-pyrrolidone, 5-methyl-2-pyrrolidone, and the like are exemplified.
  • pH adjusting agent for example, potassium dihydrogen phosphate, disodium hydrogen phosphate, sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia, diethanolamine, triethanolamine, triisopropanolamine, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, and the like are exemplified.
  • preservative and the fungicide for example, sodium benzoate, pentachlorophenol sodium, 2-pyridinethiol-1-oxide sodium, sodium sorbate, sodium dehydroacetate, 1,2-dibenzisothiazolin-3-one are exemplified.
  • proxel XL2, proxel GXL all are trade names, manufactured by Avecia Ltd.
  • Denisaido CSA, NS-500W all are trade names, manufactured by Nagase ChemteX Corporation
  • anticorrosive agent for example, benzotriazole and the like are exemplified.
  • ethylene diamine tetraacetic acid and the salts thereof diisodium dihydrogen ethylenediamine tetraacetate salt, and the like
  • iminodisuccinic acid and the salts thereof and the like are exemplified.
  • the color ink composition which is used in the ink jet recording method according to an embodiment of the invention contains at least one of the coloring material of the color system, a urethane-based resin and/or an acryl-based resin, and water.
  • the coloring material of the color system means coloring materials other than the coloring material of the white color base described above, for example, a dye, a pigment, and the like are exemplified.
  • the content of the coloring material is preferably 1% by mass to 20% by mass, and is more preferably 1% by mass to 15% by mass, with respect to the total mass of the color ink.
  • the dye and the pigment of those described in the specifications of U.S. Patent Application Publication No.2010/0086690 , U.S. Patent Application Publication No.2005/0235870 , and International Publication No. WO 2011/027842 may be suitably used.
  • the pigment is further preferably included.
  • the pigment from the viewpoint of the preservation stability such as light resistance, weather resistance, and gas resistance and the like, is preferably one or more organic pigments.
  • azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelated azo pigments, polycyclic pigments such as phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, dye chelates, dye lakes, nitro pigments, nitroso pigments, aniline black, daylight fluorescence pigments, carbon black, and the like are used.
  • the above-pigments may be used alone, or two or more kinds thereof may be used by being mixed with each other.
  • the dye for example, various dyes which are used in normal ink jet recording, such as direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, disperse dyes, vat dyes, soluble vat dyes, and reactive disperse dyes may be used.
  • the color ink composition used in the method according to an embodiment of the invention preferably contains the resin.
  • a preferable resin is at least any one of the urethane-based resin and the acryl-based resin. Since the adhesion to the urethane-based resin which is included in the white color-based ink composition described above is excellent, these resins may improve the fixity of the color image on the flexible packing film. In particular, when the urethane-based resin is contained in the color ink composition, the fixity of the color image may be further improved.
  • a resin which has Tg higher than that of the urethane resin of the white color-based ink composition in order to enhance the abrasion resistance of the color image as the urethane resin or the acrylic resin described above which is included in the color ink composition.
  • the same urethane-based resin as in the "3.1.2 Urethane-based resin" described above may be used as the urethane-based resin.
  • a resin of which Tg is 10°C to 120°C is preferably used, and a resin of which Tg is 20°C to 110°C is more preferably used.
  • Tg of the urethane-based resin is in the above-range, particularly not less than the lower limit, while imparting a moderate flexibility to the coating of the color image, it is possible to improve the abrasion resistance of the color image.
  • Tg of the urethane-based resin is in the above-range, particularly not more than the upper limit, since the coating of the color image may be firm, while suppressing the embrittlement of the coating, it is possible to improve the peeling resistance of the color image.
  • the content of the urethane-based resin is preferably 0.1% by mass to 25% by mass, is more preferably 0.5% by mass to 20% by mass, and is particularly preferably 1% by mass to 15% by mass in terms of solid content, with respect to the total mass of the color ink composition.
  • the content of the urethane-based resin is in the above range, particularly, not less than the lower limit, it is possible to further improve the abrasion resistance and the peeling resistance of the color image.
  • the content of the urethane-based resin is in the above-range, particularly is not more than the upper limit, there is a tendency that the preservation stability and the discharge stability of the color ink composition become excellent.
  • the urethane-based resin is preferably an emulsion type.
  • the acryl-based resin means a polymer obtained by using at least one among (meth)acrylic acid, (meth)acrylic acid ester, acrylonitrile, cyanoacrylate, acrylamide as a monomer (hereinafter, referred to as an "acryl-based monomer").
  • the acryl-based resin may be a homopolymer of an acryl-based monomer, and a copolymer of a monomer (for example, olefin, styrene, vinyl acetate, vinyl chloride, vinyl alcohol, vinyl ether, vinyl pyrrolidone, vinyl pyridine, vinyl carbazole, vinyl imidazole, vinylidene chloride, and the like) other than an acryl-based monomer.
  • the above-described copolymer may be any type among random copolymers, block copolymers, alternating copolymers, and graft copolymers.
  • "(meth)acrylic means at least one among "acrylic” and "methacrylic” corresponding to that.
  • the acryl-based resin is preferably at least one of (meth)acryl-based resins and styrene-(meta)acrylic acid copolymer-based resins, more preferably at least one of acryl-based resins and styrene-acrylic acid copolymer-based resins, and even more preferably styrene-acrylic acid copolymer-based resins.
  • the acryl-based resin is more preferably an emulsion type.
  • those obtained from a well-known material and preparation method may be used, and commercially available products may be used.
  • commercially available products include Microgel E-1002, Microgel E-5002 (all are trade names, manufactured by Nippon Paint Co., Ltd.), Boncoat 4001, Boncoat 5454 (all are trade names, manufactured by DIC Corporation), SAE1014 (trade name, manufactured by Nippon Zeon Co., Ltd.), Saibinol SK-200 (trade name, manufactured by Saiden Chemical Co., Ltd.), JONCRYL 1992, 7100, JONCRYL 390, JONCRYL 711, JONCRYL 511, JONCRYL 7001, JONCRYL 632, JONCRYL 741, JONCRYL 450, JONCRYL 840, JONCRYL 74J, JONCRYL HRC-1645J, JONCRYL 734, JONCRYL 852, JONCRYL 7600, JO
  • the resin of which Tg is 60°C to 120°C is preferably used, and the resin of which Tg is 70°C to 110°C is more preferably used.
  • Tg of the acryl-based resin is in the above-range, particularly not less than the lower limit, while imparting a moderate flexibility to the coating of the color image, it is possible to improve the abrasion resistance of the color image.
  • Tg of the acryl-based resin is in the above-range, particularly in not more than the upper limit, since the coating of the color image may be firm, while suppressing the embrittlement of the coating, it is possible to improve the peeling resistance of the color image.
  • the content of the acryl-based resin is preferably 0.1% by mass to 25% by mass, is more preferably 0.5% by mass to 20% by mass, and is particularly preferably 1% by mass to 15% by mass in terms of solid content, with respect to the total mass of the color ink composition.
  • the content of the color-based resin is in the above range, particularly, not less than the lower limit, it is possible to further improve the abrasion resistance and the peeling resistance of the color image.
  • the content of the acryl-based resin is in the above-range, particularly not more than the upper limit, there is a tendency that the preservation stability and the discharge stability of the color ink composition become excellent.
  • Water is a main medium of the color ink composition, and a component which is evaporated and scattered by drying.
  • the color ink composition according to an embodiment is, so called, a water-based ink which includes water as a main solvent (water of 50% by mass or more is contained).
  • the color ink composition may also contain components other than those described above. Since the components which may be used in the color ink composition are the same as the components in the above-described "3.1.4. Other components", description thereof will not be repeated.
  • the resin ink composition used in the method according to an embodiment of the invention contains a resin, and substantially does not contain the coloring material. Since the resin ink according to the embodiment substantially does not contain the coloring material, it is a colorless transparent liquid or a colorless semitransparent liquid.
  • the resin which is contained in the resin ink composition for example, well-known resins such as polyolefin-based resins, rosin-modified resins, terpene-based resins, polyester-based resins, polyamide-based resins, epoxy-based resins, vinyl chloride-based resins, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate-based resins and the like, the urethane-based resins described above, and the acryl-based resins and the like described above may be used.
  • resins such as polyolefin-based resins, rosin-modified resins, terpene-based resins, polyester-based resins, polyamide-based resins, epoxy-based resins, vinyl chloride-based resins, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate-based resins and the like, the urethane-based resins described above, and the acryl-based resins and the like described
  • the resin which is included in the resin ink composition is preferably a resin which has Tg higher than that of the urethane-based resin which is included in the white color-based ink composition described above.
  • the content of the resin in the resin ink composition is preferably 1% by mass to 30% by mass, and is more preferably 5% by mass to 25% by mass in terms of solid content, with respect to the total mass of the resin ink composition.
  • content of a resin which is included in the resin ink composition is in the above range, since, while improving the drying property of the coating film, the image which is formed on the flexible packing film may be sufficiently coated, it is possible to improve the abrasion resistance and the peeling resistance of the image.
  • the resin ink composition according to an embodiment preferably contains water as a main solvent.
  • the resin ink composition according to an embodiment may contain components other than the above-described. Since the components which may be used in the resin ink composition are the same as the components in "3.1.4. Other Components" described above, description thereof will not be repeated.
  • Each ink composition (white color-based ink composition, color ink composition, and resin ink composition described above) used in the method according to an embodiment of the invention is obtained by mixing the components described above in arbitrary order, and by removing impurities through filtration or the like, as necessary.
  • a mixing method of each component a method of stirring and mixing after adding material sequentially in a vessel provided with a stirring device such as a mechanical stirrer, a magnetic stirrer, or the like may be suitably used.
  • a filtration method a centrifugal filtration, a filter filtration or the like may be performed, as necessary.
  • Each ink composition is preferably an ink composition of which the surface tension is 15 mN/m to 50 mN/m at 20°C, and is more preferably 20 mN/m to 40 mN/m.
  • the surface tension may be measured, for example, using an automatic tensiometer CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.) to confirm the surface tension when a platinum plate is wet with the ink composition in an environment of 20°C.
  • the viscosity of each ink composition at 20°C is preferably 2 mPa ⁇ s to 15 mPa ⁇ s, and is more preferably 2 mPa ⁇ s to 10 mPa-s.
  • the viscosity may be measured by, for example, a viscoelasticity tester MCR-300 (trade name, manufactured by Pysica Inc.) in an environment of 20°C.
  • the ink jet recording method according to the present invention is performed with respect to the flexible packing film.
  • the flexible packing film is a film material having rich flexibility to be used in food packing, toiletries packing, cosmetics packing, or the like.
  • a material having an anti-fogging property and an antistatic property, and antioxidant are preferably present in the film surface.
  • the film material has a thickness in the range of 5 ⁇ m to 70 ⁇ m (preferably, 10 ⁇ m to 50 ⁇ m).
  • anionic surfactants As material having the antifogging property and the antistatic property, anionic surfactants, nonionic surfactants, cationic surfactants or vinyl-based polymers, and acryl-based polymers are commonly used.
  • surfactants fatty acid esters such as glycerine fatty acid esters, polyglycerine fatty acid esters, and sorbitan fatty acid esters, fatty acid amides such as oleic acid amide and stearic acid amide, and surfactants (fat-soluble surfactant) of fatty acids or aliphatic derivatives such as ethylene oxide adducts thereof are exemplified.
  • surfactants fatty acid esters such as glycerine fatty acid esters, polyglycerine fatty acid esters, and sorbitan fatty acid esters, fatty acid amides such as oleic acid amide and stearic acid amide, and surfactants (fat-soluble surfactant) of fatty acids or
  • acrylic polymer acrylic polymer having ethylene oxide and polar groups (hydroxyl group, carboxyl group and the like) or the like is exemplified.
  • the disclosure of patent publications for example, a method for using glycerin mono-fatty acid esters and an organic phosphite in combination ( JP-A-58-79042 ), a method for using an anti-fogging agent and a fluorine-containing compound thereof in combination ( JP-A-3-215562 ), a method for using a hindered amine-based compound ( JP-A-4-272946 ), a method for using aliphatic alcohol having 6 to 30 carbon atoms or aliphatic amine having 6 to 30 carbon atoms ( JP-A-9-31242 ), and a method for using phosphoric acid-based compounds ( JP-A-2008-115218 ) are exemplified.
  • antioxidants such as dibutyl
  • thioether-based antioxidants such as dilauryl thiopropionate
  • phosphoric acid ester-based antioxidants are exemplified. More specific examples include 3,5-di-t-butyl-4-hydroxybenzyl phosphonate-diethyl ester, N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxyhydrocinnamide), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate], tetrakis[methylene-3 (3',5'-di-t-butyl-4'-hydroxyphenyl) propionate)] methane, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butyl
  • Ester-based resins, amide-based resins, aramid-based resins, olefin-based resins, carbonate-based resins, styrene-based resins, acetal-based resins and the like may be used as the material which configures the recording surface of the flexible packing film.
  • a film substrate which includes the recording surface of the flexible packing film the above resin processed into a film or a sheet may be used.
  • any one of an unstretched film, or a stretched film which is stretched in a uniaxial direction or biaxial directions may be used, and the film or the sheet which is stretched in the biaxial directions may be preferably used.
  • it may be also used in a stacked state in which the film and the sheets formed of these various polymers are bonded.
  • a water-insoluble pigment (white color-based) was used as a colorant.
  • the water-insoluble pigments black, cyan, magenta, and yellow
  • a resin dispersion pigment in which the pigment is dispersed by a resin dispersant in advance was used.
  • a pigment dispersion was prepared as follows.
  • acrylic acid-acrylic acid ester copolymer (mass average molecular mass: 25,000, acid value: 180) 4 parts by mass as the resin dispersant was added to ion-exchanged water 75 parts by mass in which 30% aqueous ammonia (neutralizer) 1 part by mass was dissolved, and was dissolved.
  • aqueous ammonia neutralizer
  • distribution treatment was performed for 10 hours using a ball mill by zirconia beads. Thereafter, after removing impurities such as coarse particles and dust by performing a centrifugal filtration using a centrifuge, white color-based pigment concentration was adjusted to be 20% by mass. Particle diameter of the white-based pigment at that time was 350 nm in average particle diameter.
  • acrylic acid-acrylic acid ester copolymer (mass average molecular mass: 25,000, acid value: 180) 7.5 parts by mass as the resin dispersant was added to ion-exchanged water 76 parts by mass in which 30% aqueous ammonia (neutralizer) 1.5 part by mass was dissolved, and was dissolved.
  • C.I. pigment black 7 as a black pigment
  • distribution treatment was performed for 10 hours using a ball mill by zirconia beads. Thereafter, after removing impurities such as coarse particles and dust by performing a centrifugal filtration using a centrifuge, black pigment concentration was adjusted to be 15% by mass. Particle diameter of the black pigment at that time was 80 nm in average particle diameter.
  • magenta pigment dispersion In the same manner as the above-described "Preparation of black pigment dispersion" other than using a magenta pigment (C.I. pigment red 122) as a pigment, a magenta pigment dispersion was obtained. Particle diameter of the magenta pigment which is included in the magenta pigment dispersion was 100 nm in average particle diameter.
  • white color-based ink compositions W1 to W8 and color ink composition sets C1 to C3 (comprisingrespective ones of black ink compositions 1 to 3, cyan ink compositions 1 to 3, magenta ink compositions 1 to 3, and yellow ink compositions 1 to 3), as material compositions shown in Table 1, were obtained.
  • Each ink composition was prepared by placing the materials shown in Table 1 in a vessel, stirring and mixing the materials for 2 hours using a magnetic stirrer, and filtering the mixture using a membrane filter having pore diameter of 5 ⁇ m to remove impurities such as dust and coarse particles.
  • all the values in Table 1 indicate % by mass, and ion-exchange water was added for the total mass of the ink composition to be 100% by mass.
  • the resin ink compositions T1 to T4 having different material compositions were obtained as material compositions shown in Table 1.
  • Each resin ink composition was prepared by placing the materials shown in Table 1 in a vessel, stirring and mixing the materials for 2 hours using a magnetic stirrer, and filtering the mixture using a membrane filter having pore diameter of 5 ⁇ m to remove impurities such as dust and coarse particles.
  • all the values in Table 1 indicate % by mass, and ion-exchange water was added for the total mass of the resin ink composition to be 100% by mass.
  • a biaxially stretched polypropylene film (recording medium PP in Table 2; trade name: Pylene film OT, model number: P2111, thickness: 20 ⁇ m, manufactured by Toyobo Co., Ltd.), and a nylon film bag (recording medium in NY in Table 2; trade name: Kyobizin, model number: X-2030, film thickness: 80 ⁇ m, manufactured by Kurilon Chemicals Co., Ltd.) were used as a recording medium (flexible packing film).
  • an ink jet printer PX-G930 (trade name, manufactured by Seiko Epson Corporation, nozzle resolution: 180 dpi) attached with a heater capable of varying the temperature in a paper guide section was used.
  • the white color-based ink compositions W1 to W5, the color ink composition sets C1 to C3, and the resin ink compositions T1 to T4 were suitably filled in the ink jet printer PX-G930. Recording was performed on the recording medium.
  • a recording pattern with resolution of horizontal resolution 720 dpi and vertical resolution 720 dpi, an image was prepared to be capable of recording fill patterns which form a full-color image on the white-based image, and fill patterns in which the full color image on the white color-based image was coated with a coating film, by 100% duty of each color, and it was used.
  • the heater setting of the printer paper guide section at the time of printing is set to "setting the temperature of the recording surface to be 40°C"
  • the wind at temperature of 40°C with respect to recorded material in recording was blown by adjusting the wind speed at the surface of the recording medium to become about 2 m/sec to 5 m/sec (corresponding to the white color-based image heating step, the color image heating step, and the coating film heating step).
  • the drying treatment was performed by setting drying time (heating and blowing) to two minutes.
  • drying treatment was performed (corresponding to the entire heating step) by blowing the wind at temperature of 40°C or 80°C for 10 minutes of which the wind speed at the surface of the recording medium was adjusted to become about 6 m/sec to 10 m/sec.
  • the heating temperature described in Table 2 and 3 is the temperature of a step which corresponds to the entire heating step.
  • hydrophilic treatment with respect to a recording medium was performed using an internally produced corona discharge treatment machine under the condition of input electrode: 90 W, electrode width: 0.2 m, irradiating speed: 1 m/min (that is, amount of corona discharge: 450 W ⁇ min/m 2 ).
  • a transparent adhesive tape (trade name: transparent beauty color, manufactured by Sumitomo 3M Limited) was attached on the recording surface of the recorded material after it had been allowed to stand for 5 hours in a laboratory environment of 20°C to 25°C/40 %RH to 60 %RH, the tape was peeled off by hand, and by confirming the ink peeling of the recording surface and ink transfer states to the tape, a tape peelability (peeling resistance) was evaluated. Evaluation criteria for the tape peelability are as follows. In addition, the results are shown in Table 2.
  • a recorded material used in evaluation of the abrasion resistance was prepared in the same manner as the above-described "5.2.1. Tape Peeling Evaluation of Recorded Material”.
  • a recorded material for water-friction resistance evaluation was prepared using the same recording medium and the printer used in the above-described "5.2.1. Tape Peeling Evaluation of Recorded Material".
  • the white color-based ink compositions W1, W6 to W8 were filled in the ink jet printer PX-G930, and then recording was performed onto the recording medium.
  • the recording pattern with a resolution of horizontal resolution 720 dpi and vertical resolution 720 dpi, an image of fill pattern of 100% duty was prepared, and it was used.
  • the recorded material was wiped 5 times using a BEMCOT wipe (trade name: BEMCOT M-1, manufactured by Asahi Kasei Fibers Corporation) with the recording surface of the recorded material immersed in water.
  • BEMCOT wipe trade name: BEMCOT M-1, manufactured by Asahi Kasei Fibers Corporation
  • the ink state of the image region and ink transfer state to the BEMCOT wipe were observed after the wiping to evaluate the water-friction resistance of the recorded material. Evaluation criteria are as follows. In addition, the evaluation results are shown in Table 4.
  • the white color-based ink compositions W1, W6 to W8 described in Table 1, were filled into the printer head of the ink jet printer PX-G930 (trade name, manufactured by Seiko Epson Corporation, nozzle resolution: 180 dpi) in which the heater capable of varying temperature in the paper guide section was attached. After confirming that there was no defective filling and nozzle clogging by printing a nozzle check pattern after filling, the heater setting of the printer guide section was changed, and a printing pattern was made such that the ink discharge which discharges the ink at regular intervals may be stopped to perform the printing operation using it.
  • the discharge stability of the ink jet head of the white color-based ink composition was evaluated.
  • the heater settings of the printer paper guide section at the time of printing were set to be three types of "setting the temperature of the recording surface to be 40°C", "setting the temperature of the recording surface to be 60°C", and "setting the temperature of the recording surface to be 80°C.”
  • time interval of the presence or the absence of discharge was set to be a maximum 120 seconds.
  • the evaluation criteria are shown below.
  • the evaluation results are shown in Table 4.
  • the recording medium PP indicates the above-described biaxial stretching polypropylene film
  • the recording medium NY indicates the nylon film bag.
  • the evaluation result of Table 4 shows that when polyoxy ethylene alkyl ether-based surfactant is included in the white color-based ink composition, even when the recording medium is dried at high temperature, clogging of the nozzles is less, and the discharging stability of the ink is excellent.

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  • General Health & Medical Sciences (AREA)
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Claims (10)

  1. Procédé d'enregistrement à jet d'encre comprenant :
    l'enregistrement d'une image à base de couleur blanche (2) en déversant des gouttelettes d'une composition d'encre à base de couleur blanche à partir de buses d'une tête d'enregistrement à jet d'encre (21) sur une surface d'enregistrement d'un film d'emballage flexible (1) ; et
    l'enregistrement d'une image colorée en déversant des gouttelettes d'une composition d'encre colorée à partir de buses d'une tête d'enregistrement à jet d'encre (121) sur l'image à base de couleur blanche ;
    dans lequel la composition d'encre à base de couleur blanche contient de l'eau, une matière colorante d'une base de couleur blanche, et une résine d'uréthane, mais ne contient sensiblement pas des polyols d'alkyle ayant un point d'ébullition normal de 280°C ou plus, et
    dans lequel la composition d'encre colorée contient de l'eau et une matière colorante d'un système colorimétrique,
    caractérisé en ce que le procédé comprend en outre :
    une étape de chauffage d'une image entière consistant à chauffer au moins l'image à base de couleur blanche et l'image colorée à une température supérieure à 40°C afin de favoriser le séchage,
    dans lequel une épaisseur de pellicule du film d'emballage flexible se situe dans la plage de 5 µm à 70 µm.
  2. Procédé d'enregistrement à jet d'encre selon la revendication 1, dans lequel la composition d'encre colorée comprend au moins l'une d'entre une résine à base d'uréthane et une résine à base d'acrylique.
  3. Procédé d'enregistrement à jet d'encre selon la revendication 1 ou la revendication 2, comprenant par ailleurs :
    le revêtement de l'image colorée avec un film de revêtement formé par une composition d'encre à résine en déversant des gouttelettes de la composition d'encre à résine à partir de buses d'une tête d'enregistrement à jet d'encre (221) ; et
    une étape de chauffage du film de revêtement consistant à chauffer le film de revêtement à une température supérieure ou égale à 40°C afin de favoriser le séchage avant l'étape de chauffage de l'image entière,
    dans lequel l'étape de chauffage de l'image entière est effectuée après l'étape de chauffage du film de revêtement, et assure le chauffage de l'image à base de couleur blanche, de l'image colorée, et du film de revêtement à une température supérieure à 40°C afin de favoriser le séchage,
    dans lequel la composition d'encre à résine contient une résine, mais ne contient sensiblement pas de matière colorante, et
    dans lequel la température de transition vitreuse de la résine qui est incluse dans la composition d'encre à résine est plus élevée que la température de transition vitreuse d'une résine à base d'uréthane qui est incluse dans la composition d'encre à base de couleur blanche.
  4. Procédé d'enregistrement à jet d'encre selon l'une quelconque des revendications précédentes, dans lequel la température de transition vitreuse de la résine à base d'uréthane qui est incluse dans la composition d'encre à base de couleur blanche est de 10°C à 70°C.
  5. Procédé d'enregistrement à jet d'encre selon l'une quelconque des revendications précédentes, dans lequel la composition d'encre à base de couleur blanche contient en outre une cire, et dans lequel le point de fusion de la cire qui est incluse dans la composition d'encre à base de couleur blanche est plus élevé que la température de chauffage dans l'étape de chauffage de l'image entière.
  6. Procédé d'enregistrement à jet d'encre selon l'une quelconque des revendications précédentes, dans lequel, dans un cas où la masse juste après l'enregistrement de l'image à base de couleur blanche est fixée à 100% et la masse au moment où se termine le séchage de l'image à base de couleur blanche est fixée à 0%, l'enregistrement de l'image colorée est effectué lorsque la masse se situe dans la plage de 30% à 80% grâce au séchage de l'image à base de couleur blanche.
  7. Procédé d'enregistrement à jet d'encre selon l'une quelconque des revendications précédentes, dans lequel la composition d'encre à base de couleur blanche contient un surfactant à base de polyoxyéthylène d'alkyle éther.
  8. Procédé d'enregistrement à jet d'encre selon l'une quelconque des revendications précédentes, comprenant par ailleurs :
    avant l'enregistrement de l'image colorée, une étape de chauffage de l'image à base de couleur blanche consistant à chauffer l'image à base de couleur blanche dans la plage de 40°C à 80°C afin de favoriser le séchage,
    dans lequel la température de chauffage dans l'étape de chauffage de l'image entière est plus élevée que la température de chauffage dans l'étape de chauffage de l'image à base de couleur blanche, et
    dans lequel un temps de chauffage dans l'étape de chauffage de l'image entière est plus long qu'un temps de chauffage dans l'étape de chauffage de l'image à base de couleur blanche.
  9. Procédé d'enregistrement à jet d'encre selon l'une quelconque des revendications précédentes, dans lequel au moins l'un d'entre un agent antibuée et un agent antistatique est présent sur la surface d'enregistrement du film d'emballage flexible.
  10. Procédé d'enregistrement à jet d'encre selon l'une quelconque des revendications précédentes, dans lequel la même tête d'enregistrement à jet d'encre est utilisée pour déverser les gouttelettes de la composition d'encre à base de couleur blanche et les gouttelettes de la composition d'encre colorée.
EP13185575.1A 2012-11-09 2013-09-23 Procédé d'enregistrement à jet d'encre Active EP2730424B1 (fr)

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CN103802518A (zh) 2014-05-21
US8911074B2 (en) 2014-12-16
EP2730424A1 (fr) 2014-05-14
US20140132684A1 (en) 2014-05-15
JP2014094495A (ja) 2014-05-22

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